A study was made to modify water-soluble poly(vinyl alcohol) (PVA) by grafting acrylic acid and styrene (AAc/Sty) comonomers using gamma rays as an initiator. The factors that affect the preparation process and grafting yield were studied and more economical grafts under the most favorable reaction conditions were obtained. It was found that the high degree of grafting in such systems was obtained in the presence of an ethanol-water mixture in which water plays a significant role in enhancing the graft copolymerization. The critical amount of water to afford the maximum grafting yield was evaluated. The effect of the comonomer composition on the grafting yield was also investigated and it was observed that using a mixture of AAc/Sty monomers influences the extent of grafting of each monomer onto the PVA substrate and the phenomenon of synergism occurs during such a reaction. Also, the degree of grafting increases as the content of the solvent decreases in the reaction medium. However, the grafting yield increased as the total dose increased. The graft copolymer was characterized by IR and UV spectroscopic methods. The permeation of heavy metals such as Ni and Co through the grafted membranes was investigated and the efficiency of the separation process was also determined.